Patent EA-003995-B1 (EA)
Title: Pesticidal 1-aryl and pyridylpyrazole derivatives
Inventor: MANNING DAVID TREADWAY
IPC: C07D231/16
Filed: 1997-12-18
Abstract: 1. A 1-arylpyrazole of the formula (I): wherein: R1 is H or halogen; each of R2 and R4, which are identical or different, is H, halogen or alkyl; R3 is halogen, haloalkyl, haloalkoxy or R10S(O)m; R5 is lower alkyl, haloalkyl, alkenyl and alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; Z is hydrogen, halogen, alkyl, formyl, -C(O)alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylideneamino, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl, amino, R6NH- OR R7R8N-; each of R6, R7 and R8, which are identical or different, is alkyl-S(O)p-, formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl, alkenyl containing 3 to 6 carbon atoms, or -C(O)alkyl wherein the alkyl and alkenyl portions are optionally substituted by one or more R9; or R7 and R8 are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; R9 is cyano, nitro, alkoxy, haloalkoxy, R10S(O)q, -C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; R10 is lower alkyl or lower haloalkyl; m, n, p and q are 0, 1or 2; M is C-halo, C-CH3, C-CH2F, C-CH2Cl, C-NO2 or N, wherein if not indicated otherwise, said alkyl groups and moieties contain from 1 to 4 carbon atoms, alkenyl and alkynyl groups and moieties contain from 2 to 6 carbon atoms; or a pesticidally acceptable salt thereof; excluding 1-arylpyrazole of the formula (I), in which: R5 is haloalkyl; and Z is H, 1H-pyrrol-1-yl, amino group, or R6NH-, where R6 is formyl, alkynyl, containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkyl, alkenyl, containing from 3 to 6 carbon atoms or C(O)alkyl, where alkyl portion is optionally substituted by one or more R9, where R9 is halo; and other groups are as defined above. 2. A compound according to Claim 1, wherein R3 is halogen, haloalkyl or haloalkoxy. 3. A compound according to Claim 1 or 2, wherein R5 is alkyl. 4. A compound according to Claim 1, 2 or 3 wherein Z is amino, R6NH- or R7R8N-. 5. A compound according to Claim 1, in which: R1 is F, Cl, Br or H; R2 and R4 are H; R3 is -CF3, -OCF3, -CHF2, -S(O)mCF3, -CFCl2, -CF2Cl, -OCF2Cl, -OCFCl2, Cl, Br or F; R5 is methyl or ethyl; Z is H, halogen (F, Cl, Br), C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl; or amino, -NHR6 or -NR7R8, wherein each of R6, R7 and R8, which are identical or different, is C1-C3 alkyl, C3 alkenyl or -C(O)alkyl wherein the alkyl or alkenyl portions are unsubstituted or substituted with cyano, alkoxy, alkyl-S(O)q-, nitro, alkoxycarbonyl, -C(O)alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, hydroxy or halogen (F, Cl, Br); and M is CCl, CF, CBr or N. 6. A compound according to Claim 1, in which: R1 is Cl or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or Cl; R5 is methyl or ethyl; Z is H, halogen (F, Cl, Br), C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl; or amino, -NHR6 or -NR7R8, wherein each of R6, R7 and R8, which are identical or different, is C1-C3 alkyl, C3 alkenyl or -C(O)alkyl wherein the alkyl or alkenyl portions are unsubstituted or substituted with cyano, alkoxy, alkyl-S(O)p, nitro, alkoxycarbonyl, -C(O)alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, hydroxy or halogen (F, Cl, Br); and M is CCl, CBr or N. 7. A compound according to Claim 1, in which: R1 is Cl or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or Cl; R5 is methyl or ethyl; Z is H or amino; and M is CCl, CBr or N. 8. A compound according to Claim 1, in which: R1 is Cl or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or Cl; R5 is methyl or ethyl; Z is H or amino; and M is CCl, CBr or N. 9. A compound according to Claim 1, wherein the 1-aryl group is: 2,6-dichloro-4-trifluoromethylphenyl; 2,6-dichloro 4-trifluoromethoxyphenyl; 2-bromo-6-chloro-4-trifluoromethylphenyl; 2-bromo-6-chloro-4-trifluoromethoxyphenyl; 2,6-difluoro-4-trifluoromethylphenyl; 2-chloro4-trifluoromethylphenyl; 2,6-dichloro-3-methyl-trifluoromethylphenyl; 3-chloro-5-trifluoromethyl-2-pyridinyl; 3-chloro-5-trifluoromethoxy-2-pyridinyl; 3,5-dichloro-2-pyridinyl; 2,6-dichloro-4-bromophenyl; 2,4,6-trichiorophenyl; 2-bromo-6-fluoro-4-difluoromethylphenyl; 2-chloro-6-fluoro-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethylphenyl; 2,6-dibromo4-trifluoromethoxyphenyl; or 2-bromo4-trifluoromethylphenyl. 10. A compound according to Claim 1, wherein Z is acetylamino, amino, 2-n-butoxypropionylamino, methyl, hydroxyacetylamino, ethyl, 3-ethylsulfinylpropylamino, bromo, formylamino, chloro, methylamino, ethylamino, 2-hydroxyethylamino, 2-methoxyethylamino, methylsulfonylamino, 2-ethylsulfonylethylamino, 4-methoxybenzoylamino, 2-cyanoethylamino, 4-methoxybenzylamino, 2-methylthioethylamino, 2-aminocarbonylethylamino, 2-methylsulfinylethylamino, 3-methoxycarbonylpropylamino, 2-ethylsulfinylethylamino, 2-methylsulfonylethylamino, cyanomethylamino, 2-ethylthioethylamino, aminocarbonylmethylamino, dimethylamino, 2-nitroethylamino, 2-acetylethylamino, methylcarbonylmethylamino, methoxycarbonylamino, or ethoxycarbonylamino. 11. A compound according to Claim 1, wherein-S(O)nR5 is methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl or isopropylthio. 12. The compound of formula (I) according to Claim 1, which is: 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methylthiopyrazole-3-thiocarboxamide; 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methylsulfinylpyrazole-3-thiocarboxamide; 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methysulfonylpyrazole-3-thiocarboxamide; 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole-3-thiocarboxamide; 5-amino-1-(2-bromo-6-chloro-4-trifluoromethylphenyl)-4 methylsulfinylpyrazole-3-thiocarboxamide; 5-amino-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-methylsulfinylpyrazole-thiocarboxamide; 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-ethylsulfinylpyrazole-3-thiocarboxamide; 5-amino-1-(2-chloro-4-trifluoromethylphenyl)-4-methylsulfinylpyrazole-3-thiocarboxamide; 5-amino-1-(2-bromo-6-chloro-4-trifluoromethylphenyl)-4-ethylsulfinylpyrazole 3-thiocarboxamide; or 5-amino-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-ethylsulfinylpyrazole-3-thiocarboxamide. 13. The compound of formula (I) according to Claim 1, which is: 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole-3-thiocarboxamide; or 4-dichlorofluoromethylsulfonyl-1-(2,4,6-trichlorophenyl)pyrazole-3-thiocarboxamide. 14. A pesticidal composition comprising a pesticidally effective amount of 1-arylpyrazole according to any one of Claims 1 to 13 or a pesticidally acceptable salt 1-arylpyrazole of formula (I) in association with an agriculturally acceptable inert carrier thereof. 15. A pesticidal composition according to Claim 14 which contains from about 0.05 to about 95% (by weight) of a compound of formula (I). 16. A pesticidal composition according to Claim 14 which contains from about 0.00005 to about 90% (by weight) of a compound of formula (I). 17. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of 1-arylpyrazole according to any one of Claims 1 to 13, or a pesticidally acceptable salt 1-arylpyrazole of formula (I) according to any one of claims 14, 15 and 16. 18. The method according to Claim 17, wherein said pests are insects. 19. The method according to Claim 18, wherein said insects are sucking insects. 20. The method according to Claim 17, wherein said locus is a crop area. 21. The method according to Claim 20, wherein said compound is applied to said locus at a rate of from about 5g to about 1 kg/ha. 22. The method according to Claim 17, wherein said locus is an animal. 23. The method according to Claim 22, wherein said compound is applied to said locus at a rate of from about 0.1 to 20mg per kg body weight of the animal per day. 24. A method for controlling pests of vertebrates comprising applying to said animals of 1-arylpyrazole of formula (I) as defined in claim 1 or a pesticidally acceptable salt thereof at a unit dosage of about from 0.1 to 100mg per kg body weight of the animal per day. 25. A process for preparing a compound of formula (I) as defined in Claim 1 which comprises the reaction of a compound of formula (II): where R1, R2, R3, R4, R5, M, n and Z are as defined in Claim 1, with an alkali or alkaline earth metal hydrosulfide. 26. A process for preparing a compound of formula (I), in which Z is alkoxycarbonyl or alkylthiocarbonyl, comprising esterification of the corresponding compound of formula (I) in which Z is carboxy with an alcohol of formula (V): R12OH (V) or an thiol of formula (VI): R12SH (VI) wherein R12 in formulae (V) and (VI) is alkyl. 27. A process for preparing a compound of formula (I), in which Z is -C(O)alkyl, comprising oxidation of the corresponding formula (VIII): where R1, R2, R3, R4, R5, M, n and Z are as defined in Claim 1 and R14 is alkyl. 28. The process according to any one of claims 25-27, further comprising a step of the conversion of the compound thus obtained of formula (I) according to claim 1, selected from: a) the oxidation of the corresponding compounds of formula (I) in which n is 1 or 2; b) the alkylation of the corresponding compound of formula (I) wherein Z is amino with a compound of formula (III): R9-CH=CH2 (III) wherein R9 is as defined in Claim 1 obtaining the compound (I), in which Z is R6NH-, wherein R6 is ethyl substituted at the 2-position by R9 in which R9 is cyano, nitro, -S(O)qR10, -C(O)alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; c) alkylation of the corresponding compound of formul